US11515570B2 - Secondary battery - Google Patents

Secondary battery Download PDF

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US11515570B2
US11515570B2 US16/865,462 US202016865462A US11515570B2 US 11515570 B2 US11515570 B2 US 11515570B2 US 202016865462 A US202016865462 A US 202016865462A US 11515570 B2 US11515570 B2 US 11515570B2
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electrode plate
positive electrode
negative electrode
solid electrolyte
secondary battery
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US20200266494A1 (en
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Yukihisa Takeuchi
Iwao OWADA
Yukinobu Yura
Yosuke Sato
Toshihiro Yoshida
Yuji Katsuda
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NGK Insulators Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a secondary battery.
  • the batteries in such applications contain liquid electrolytes (i.e., electrolytic solutions) of, for example, flammable organic diluting solvents that functions as media for ion migration.
  • the batteries including such electrolytic solutions have several problems, such as leakage, combustion and explosion of the electrolytic solution.
  • secondary all-solid batteries have been developed that contain solid electrolytes in place of liquid electrolytes and all the other components composed of solid material. Since the electrolytes are composed of solid material, the secondary all-solid batteries have little risk of combustion and barely cause these problems, such as leakage of liquid material and deterioration of battery performance due to corrosion.
  • PTL 1 JP2016-66550A discloses a secondary all-solid battery having stable charge/discharge characteristics at high temperature.
  • the battery includes a solid electrolyte composed of a first layer having a NASICON structure containing Li, Al, Ti, and P and a second layer having another NASICON structure containing Li, Al, M (where M is Ge or Zr) and P, and no Ti.
  • This literature also discloses production of a secondary all-solid battery that includes a positive electrode layer having a thickness of 9 ⁇ m, a negative electrode layer having a thickness of 12 ⁇ m, and a solid electrolyte layer having a thickness of 12 ⁇ m.
  • PTL 2 JP2015-185337A discloses an all-solid battery including a positive electrode, a negative electrode, and a solid electrolyte layer, the positive electrode or negative electrode being composed of a lithium titanate (Li 4 Ti 5 O 12 ) sintered body.
  • PTL 3 discloses a lithium secondary battery including a solid electrolyte and an oriented positive electrode plate that contains a plurality of primary grains composed of lithium complex oxide, such as lithium cobaltate (LiCoO 2 ), where the primary grains are oriented at a mean orientation angle of more than 0° to 30° to a main face of the positive electrode plate.
  • lithium complex oxide such as lithium cobaltate (LiCoO 2 )
  • the secondary all-solid battery disclosed in PTL 1 is disadvantageous in low capacity or low energy density.
  • the secondary all-solid battery disclosed in PTL 2 also has a problem in that the battery is significantly deteriorated during operations under high-temperature conditions.
  • a secondary battery including a positive electrode plate and a negative electrode plate each composed of an inorganic material including oxide and having a thickness of 25 ⁇ m or more, and an inorganic solid electrolyte layer can have large battery capacity and superior cycle capacity retention in rapid charge/discharge cycles at a temperature of 100° C. or higher.
  • an object of the present invention is to achieve large battery capacity and superior cycle capacity retention in rapid charge/discharge cycles in a secondary battery.
  • a secondary battery comprising:
  • a method of using a secondary battery comprising the steps of:
  • FIG. 1 is a schematic cross-sectional view illustrating a secondary battery of the present invention.
  • FIG. 2 is an SEM image illustrating an exemplary cross-section perpendicular to a main face of an oriented positive electrode plate.
  • FIG. 3 is an EBSD image in the cross-section of the oriented positive electrode plate shown in FIG. 2 .
  • FIG. 4 is an area-based histogram illustrating the distribution of orientation angles of primary grains in the EBSD image shown in FIG. 3 .
  • the present invention relates to a secondary battery.
  • the term “secondary battery” refers to as a battery that can be repeatedly charged and discharged in a broad sense, and any battery that includes a positive electrode plate, a negative electrode plate, and a solid electrolyte layer each composed of an inorganic material as described later.
  • Examples of such a secondary battery include a secondary lithium battery (also referred to as a secondary lithium ion battery), a secondary sodium ion battery, a secondary magnesium ion battery, and a secondary aluminum ion battery, and preferred is a secondary lithium ion battery.
  • FIG. 1 schematically illustrates an exemplary secondary battery of the present invention.
  • the secondary battery 10 shown in FIG. 1 includes a positive electrode plate 12 , an inorganic solid electrolyte layer 14 , and a negative electrode plate 16 .
  • the positive electrode plate 12 is composed of an inorganic material containing a positive electrode active material in an oxide form.
  • the negative electrode plate 16 is composed of an inorganic material containing a negative electrode active material in an oxide form.
  • the positive electrode plate 12 and the negative electrode plate 16 each have a thickness of at least 25 ⁇ m.
  • the secondary battery 10 is charged and discharged at a temperature of 100° C. or higher.
  • the positive electrode plate 12 and the negative electrode plate 16 each composed of an inorganic material containing oxide and the inorganic solid electrolyte layer 14
  • the positive electrode plate 12 and the negative electrode plate 16 each having a thickness of at least 25 ⁇ m and the charge/discharge cycles at a temperature of 100° C. or higher result in large battery capacity, and superior cycle capacity retention in rapid charge/discharge cycles of the secondary battery 10 .
  • the positive electrode plate 12 and the negative electrode plate 16 each have large thickness as described above, the secondary battery 10 can exhibit the large battery capacity.
  • the positive electrode plate 12 and the negative electrode plate 16 which are composed of ceramic material, can have an increased thickness as needed, resulting in large capacity and high energy density.
  • the secondary battery 10 is charged and discharged at an operational temperature of 100° C. or higher, preferably 100 to 300° C., more preferably 100 to 200° C., further more preferably 100 to 150° C.
  • a heating means achieving such an operational temperature include various heaters and devices that generate heat.
  • Preferred examples of the heating means include electroconductive ceramic heaters.
  • the secondary lithium battery of the present invention is preferably provided as a secondary battery system including a heating means.
  • the positive electrode plate 12 is composed of inorganic material, and the inorganic material contains a positive electrode active material in an oxide form.
  • the positive electrode active material in the oxide form may be appropriately selected depending on the type of secondary battery 10 , and is not particularly limited.
  • the positive electrode active material is preferably lithium complex oxide in secondary lithium ion battery.
  • the lithium complex oxide is an oxide represented by Li x MO 2 (0.05 ⁇ x ⁇ 1.10, M is at least one transition metal, and M typically contains at least one selected from the group of Co, Mn and Al).
  • the lithium complex oxide has a layered rock salt structure.
  • the layered rock salt structure is a crystal structure in which a lithium layer and a transition metal layer other than lithium are alternately stacked with an oxygen layer therebetween, i.e., a crystal structure in which a transition metal ion layer and a lithium single layer are alternately stacked with oxide ions therebetween (typically an ⁇ -NaFeO 2 structure, i.e., a structure in which transition metals and lithium metals are regularly disposed along the [111] axis of a cubic rock salt structure).
  • ⁇ -NaFeO 2 structure i.e., a structure in which transition metals and lithium metals are regularly disposed along the [111] axis of a cubic rock salt structure.
  • lithium complex oxides include Li x CoO 2 (lithium cobaltate), Li x NiO 2 (lithium nickelate), Li x MnO 2 (lithium manganate), Li x NiMnO 2 (lithium nickel manganate), Li x NiCoO 2 (lithium nickel cobaltate), Li x CoNiMnO 2 (lithium cobalt nickel manganate), Li x CoMnO 2 (lithium cobalt manganate), and solid solutions of Li 2 MnO 3 and the above compounds, and particularly preferably, Li x CoO 2 (lithium cobaltate, typically LiCoO 2 ).
  • the lithium complex oxide may contain at least one element selected from Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, Sb, Te, Ba, Bi, and W.
  • the lithium complex oxide having another crystal structure is suitably used, such as LiMn 2 O 4 and LiNi 0.5 Mn 1.5 O 4 having a spinel structure, and LiMPO 4 having an olivine structure (where M is at least one selected from Fe, Co, Mn and Ni).
  • the positive electrode plate 12 is preferably a sintered plate (e.g., a lithium complex oxide sintered plate).
  • the positive electrode plate contains no binder and thereby exhibits high packing density of the positive electrode active material (e.g., lithium complex oxide), resulting in a large capacity and high charge/discharge efficiency.
  • the positive electrode plate contains no binder for the reason that the binder disappears or burns off during firing even if the green sheet contains the binder.
  • the positive electrode plate 12 is preferably an oriented positive electrode plate that includes a plurality of primary grains composed of lithium complex oxide, the primary grains being oriented at a mean orientation angle of more than 0° to 30° to a main face of the positive electrode plate.
  • Such an oriented positive electrode plate can be manufactured in accordance with the method disclosed in PTL 3 (WO2017/146088).
  • FIG. 2 illustrates an exemplary cross-sectional SEM image perpendicular to a main face of the oriented positive electrode plate
  • FIG. 3 illustrates a cross-sectional electron backscatter diffraction (EBSD) image perpendicular to a main face of the oriented positive electrode plate.
  • EBSD cross-sectional electron backscatter diffraction
  • FIG. 4 is an area-based histogram illustrating the distribution of orientation angles of primary grains 11 in the EBSD image of FIG. 3 .
  • discontinuity of the crystal orientation can be observed.
  • the orientation angle of each primary grain 11 is determined by the shade of color, and a darker shade indicates a smaller orientation angle.
  • the orientation angle is a tilt angle between the (003) plane of each primary grain 11 and a main face of the plate.
  • black portions inside the oriented positive electrode plate 12 indicate pores.
  • the positive electrode plate 12 is preferably an oriented sintered plate composed of a plurality of primary grains 11 bonded to each other.
  • Each primary grain 11 is mainly in a platy shape, and may be formed in, for example, a cuboid shape, a cubic shape, and a spherical shape.
  • the cross-sectional shape of each primary grain 11 may be a rectangle, a polygon other than a rectangle, a circle, an ellipse, or any other complicated shape.
  • the averaged value of the orientation angles i.e., the mean orientation angle of primary grains 11 composed of lithium complex oxide is preferably more than 0° to 30°.
  • This angle range can further reduce the deterioration of battery in operating at high temperature, and provides the following advantages 1) to 3).
  • the expansion and contraction of the oriented positive plate 12 accompanied by the expansion and contraction of each primary grain 11 in the direction perpendicular to the (003) plane depending on intercalation and deintercalation of lithium ions can be decreased in the main face direction by smaller orientation angle of the (003) plane to the main face direction of the main face, resulting in a reduction in stress generated between the oriented positive plate 12 and the inorganic solid electrolyte 14 . 3)
  • the high-rate performance can be further improved.
  • This further improvement is caused by smooth intercalation and deintercalation of lithium ions in the oriented positive electrode 12 , because the expansion and contraction of oriented positive electrode plate 12 proceeds more dominantly in the thickness direction than in the main face direction of the main face and thereby carrier ions (e.g., lithium ions) can intercalate and deintercalate smoothly.
  • carrier ions e.g., lithium ions
  • the mean orientation angle of primary grains 11 composed of lithium complex oxide is determined through (i) polishing of the positive electrode plate with a cross section polisher (CP), (ii) EBSD analysis of the resultant cross-section of oriented positive electrode plate at a specific magnification (e.g., 1000 folds) and a specific field of view (e.g., 125 ⁇ m by 125 ⁇ m), (iii) measurement of angles between the (003) plane of primary grains and a main face of positive electrode plate (i.e., tilt of crystal orientation from the (003) plane) as orientation angles based on all grains specified in the resultant EBSD image, and (iv) averaging of all the resulting angles to be a mean orientation angle.
  • CP cross section polisher
  • the mean orientation angle of the primary grains 11 is preferably 30° or less, and more preferably 25° or less from the viewpoint of a further improvement in high-rate performance.
  • the mean orientation angle of the primary grains 11 is preferably 2° or more, and more preferably 5° or more from the viewpoint of a further improvement in high-rate performance.
  • the orientation angle of each primary grain 11 composed of lithium complex oxide may be widely distributed from 0° to 90°, and most of the orientation angles are preferably distributed in a region of more than 0° to 30°.
  • the total area of primary grains 11 that have the orientation angle of more than 0° to 30° to a main face of the oriented positive electrode plate 12 (hereinafter, referred to as low-angle primary grains) is preferably 70% or more, and more preferably 80% or more of the total area of the primary grains 11 included in the cross-section (specifically, 30 primary grains 11 used in calculation of the mean orientation angle).
  • the total area of the low-angle primary grains having an orientation angle of 20° or less is more preferably 50% or more of the total area of the 30 primary grains 11 used in the calculation of the mean orientation angle.
  • the total area of the low-angle primary grains having an orientation angle of 10° or less is more preferably 15% or more of the total area of the 30 primary grains 11 used in the calculation of the mean orientation angle.
  • each primary grain 11 composed of lithium complex oxide is mainly platy
  • the cross-section of each primary grain 11 respectively extends in a predetermined direction as shown in FIGS. 2 and 3 , and typically has a substantially rectangular shape.
  • the total area of primary grains 11 that have an aspect ratio of 4 or more among the primary grains 11 included in the analyzed cross-section is preferably 70% or more, and more preferably 80% or more of the total area of the primary grains 11 included in the cross-section (specifically, 30 primary grains 11 used in calculation of the mean orientation angle).
  • the aspect ratio of the primary grains 11 is a value determined by dividing the maximum Feret diameter by the minimum Feret diameter of the primary grains 11 .
  • the maximum Feret diameter is the maximum distance between two parallel straight lines by which the primary grains 11 are sandwiched in the EBSD image from cross-sectional observation.
  • the minimum Feret diameter is the minimum distance between two parallel straight lines by which the primary grains 11 are sandwiched.
  • a plurality of primary grains constituting the oriented sintered plate has a mean grain diameter of 5 ⁇ m or more.
  • 30 primary grains 11 used in calculation of the mean orientation angle have a mean grain diameter of preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, further more preferably 12 ⁇ m or more.
  • This diameter range can reduce the number of grain boundaries between the primary grains 11 in the direction where lithium ions conduct, resulting in an improvement in the overall ion conductivity and thereby a further enhancement in high-rate performance.
  • the mean grain diameter of the primary grains 11 is a value determined by the arithmetic average of the equivalent circle diameters of the respective primary grains 11 .
  • the equivalent circle diameter indicates the diameter of a circle having an identical area as each primary grain 11 in the EBSD image.
  • a plurality of primary grains constituting the oriented sintered plate has a mean grain diameter of 20 ⁇ m or less.
  • the primary grains 11 has a mean grain diameter of preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
  • Such a diameter range can reduce the distance for lithium ions to travel in the primary grains 11 , resulting in a further improvement in high-rate performance.
  • the lithium ions move from the inside of primary grains 11 to the solid electrolyte filled in the pores of the positive electrode, further pass through the film-shaped (or planar) solid electrolyte 14 and move into the grains of negative electrode as a counter electrode.
  • the mean grain diameter of primary grains 11 can be measured by analysis of a cross-sectional SEM image of the sintered plate.
  • the sintered plate is processed with a cross section polisher (CP) to expose a polished cross-section.
  • the polished cross-section is observed by SEM (scanning electron microscopy) at a specific magnification (e.g., 1000 folds) and a specific field of view (e.g., 125 ⁇ m by 125 ⁇ m).
  • the field of view is selected such that 20 or more primary grains are located in this field.
  • circumscribed circles are drawn for all primary grains and the diameters of circumscribed circles are measured and averaged to be a mean grain diameter of primary grains.
  • the positive electrode plate 12 preferably includes pores.
  • the pores included in the positive electrode plate 12 can satisfactorily (or uniformly) relax the stress generated by expansion and contraction of crystal lattices accompanied by intercalation and deintercalation of carrier ions (e.g., lithium ions) during charge/discharge cycles. This stress relaxation can effectively reduce the cracking at the grain boundaries accompanied by the repeated charge/discharge cycles.
  • a plurality of pores included in the positive electrode plate 12 is preferably oriented from the viewpoint of a further enhancement in the above advantages. The orientation of the pores can be achieved, for example, by the use of raw grains having platy crystals. In particular, the above advantages can be remarkably enhanced in high-rate charge/discharge cycles at a high temperature.
  • the positive electrode plate 12 has a mean pore aspect ratio of at least 1.2, preferably at least 1.5, further preferably at least 1.8. It is conceivable that the anisotropy in the pore shape defined by such an aspect ratio can advantageously release the flexure stress and the stress occurring in charge/discharge cycles, resulting in superior performances, such as high bending resistance and rapid charge characteristics.
  • the mean pore aspect ratio may have any upper limit.
  • the mean pore aspect ratio is preferably 30 or lower, more preferably 20 or lower, and further more preferably 15 or lower.
  • the mean pore aspect ratio in the positive electrode plate 12 indicates the averaged value of the aspect ratios of the pores in the positive electrode plate 12 , and the aspect ratio of the pores is defined by the ratio of the length of pores in the longitudinal direction to the length of pores in the lateral direction.
  • the mean pore aspect ratio can be determined by the analysis of a cross-sectional SEM image of the positive electrode plate 12 , as will be explained in detail in Examples described later.
  • the positive electrode plate 12 has a porosity of preferably 2 to 20%, more preferably 3 to 20%, further more preferably 5 to 18%. Such a porosity range can desirably achieve both advantages of stress relaxation due to the pores and increased battery capacity.
  • the porosity in the positive electrode plate 12 is a volume rate of pores (including open pores and closed pores) in the positive electrode plate 12 , and can be determined by the analysis of a cross-sectional SEM image of the positive electrode plate 12 , as will be explained in detail in Examples described later.
  • the positive electrode plate 12 has a porosity of preferably 10 to 50%, more preferably 10 to 40%, further more preferably 12 to 35%.
  • a porosity range is advantageous in filling the pores included in the positive electrode plate 12 with the inorganic solid electrolyte.
  • a more compact positive electrode plate leads to slower diffusion of lithium in the positive electrode plate, and thereby the discharge capacity that the positive electrode plate can inherently provide cannot be achieved.
  • the electrolyte can assist the diffusion of lithium in the positive electrode plate, resulting in an increase in discharge capacity.
  • the inorganic solid electrolyte occupies preferably part of the pores, more preferably at least 70% of the pores, further more preferably at least 85% of the pores in the positive electrode plate 12 .
  • a higher filling rate of the inorganic solid electrolyte in the pores of the positive electrode plate 12 is preferred. Although the rate is ideally 100%, it is practically 99% or lower.
  • the positive electrode plate 12 preferably consists of the inorganic solid electrolyte and the positive electrode active material. In other words, the addition of an electron conductive aid in the positive electrode plate leads to a decrease in the weight of active material and the battery capacity. In contrast, the use of the sintered plate in the positive electrode plate requires no electron conductive aid and can ensure desirable electron conductivity only by the positive electrode active material.
  • This improvement in electron conductivity is caused by strong connection through necking between the grains constituting the sintered plate (i.e., grains of positive electrode active material). Furthermore, the use of the sintered plate can appropriately decrease the pores in the positive electrode plate (i.e., the pores lead to a reduction in capacity), and thereby increase the energy density of the battery.
  • the positive electrode plate 12 has a thickness of at least 25 ⁇ m, preferably at least 30 ⁇ m, more preferably at least 40 ⁇ m, particularly more preferably at least 50 ⁇ m, most preferably at least 55 ⁇ m from the viewpoint of an increase in the active material capacity per unit area and an improvement in the energy density of lithium secondary battery 10 .
  • the upper limit of the thickness is not particularly limited.
  • the positive electrode plate 12 has a thickness of preferably less than 500 ⁇ m, more preferably 400 ⁇ m or less, further more preferably 300 ⁇ m or less, particularly preferably 250 ⁇ m or less, particularly more preferably 200 ⁇ m or less from the viewpoint of delayed deterioration in battery characteristics (in particular, an increase in resistance value) accompanied by charge/discharge cycles.
  • the positive electrode plate 12 has dimensions of preferably 5 mm by 5 mm or more, more preferably 10 mm by 10 mm or more, and in another expression, an area of preferably 25 mm 2 or more, more preferably 100 mm 2 or more.
  • the negative electrode plate 16 is composed of an inorganic material that contains a negative electrode active material in an oxide form.
  • the negative electrode active material in an oxide form may be selected depending on the type of secondary battery 10 , and may be any oxide material but preferably an oxide material containing at least Ti.
  • preferred examples of such a negative electrode active material include lithium titanate Li 4 Ti 5 O 12 (hereinafter referred to as “LTO”), niobium titanium complex oxide Nb 2 TiO 7 , and titanium oxide TiO 2 . More preferred examples of the negative electrode active material include LTO and Nb 2 TiO 7 .
  • Typical LTO is known to have a spinel structure. Alternatively, LTO may have a different structure during the charge/discharge cycles of the battery.
  • LTO may have two phases consisting of Li 4 Ti 5 O 12 having a spinel structure and Li 7 Ti 5 O 12 having a rock-salt structure during the charge/discharge cycles, and the reaction continues between the two phases.
  • LTO may have any structure other than the spinel structure.
  • the negative electrode plate 16 is preferably composed of a sintered plate containing, for example, LTO or Nb 2 TiO 7 . Since the negative electrode plate composed of a sintered plate contains no binder, high capacity and satisfactory charge/discharge efficiency can be achieved due to a high packing density of the negative electrode active material, for example, LTO or Nb 2 TiO 7 . The binder in the green sheet will eventually disappear or burn off while the green sheet is fired into the negative electrode plate.
  • the LTO sintered plate can be produced by a process disclosed in PTL 2 (JP2015-185337A).
  • the negative electrode plate 16 preferably includes pores.
  • the pores included in the negative electrode plate 16 can satisfactorily (or uniformly) relax the stress occurring in expansion and contraction of crystal lattices accompanied by intercalation and deintercalation of carrier ions (e.g., lithium ions) in charge/discharge cycles. This stress relaxation can effectively reduce the cracking at the grain boundaries accompanied by the repeated charge/discharge cycles.
  • carrier ions e.g., lithium ions
  • the negative electrode plate 16 has a porosity of preferably 2 to 20%, more preferably 3 to 20%, further more preferably 5 to 18%. Such a porosity range can desirably achieve both advantages of stress relaxation due to the pores and increased battery capacity.
  • the porosity in the negative electrode plate 16 is a volume rate of pores (including open pores and closed pores) in the negative electrode plate 16 , and can be determined by the analysis of a cross-sectional SEM image of the negative electrode plate 16 , as will be explained in detail in Examples described later.
  • the negative electrode plate 16 has a porosity of preferably 10 to 50%, more preferably 10 to 40%, further more preferably 12 to 35%. This porosity range is advantageous in filling the pores contained in the negative electrode plate 16 with the inorganic solid electrolyte.
  • a more compact negative electrode plate leads to slower diffusion of lithium in the negative electrode plate, and thereby the discharge capacity that the negative electrode plate can inherently have cannot be achieved.
  • the electrolyte facilitates the diffusion of lithium, resulting in an enhancement in the resultant discharge capacity.
  • the pores contained in the negative electrode plate 16 are preferably filled with the inorganic solid electrolyte.
  • the inorganic solid electrolyte occupies into more preferably at least 70%, further more preferably at least 85% of the pores contained in the negative electrode plate 16 .
  • a higher filling rate of the inorganic solid electrolyte into the pores of the negative electrode plate 16 is preferred. Although the rate is ideally 100%, it is practically 99% or lower.
  • the negative electrode plate 16 preferably consists of the inorganic solid electrolyte and the negative electrode active material. In other words, the addition of the electron conductive aid in the negative electrode plate leads to a decrease in the weight of active material and the battery capacity.
  • the use of the sintered plate in the negative electrode plate requires no electron conductive aid, in other words, only the inorganic solid electrolyte and the active material can achieve desirable electron conductivity.
  • This improvement in electron conductivity is caused by strong connection through necking between the grains constituting the sintered plate (i.e., grains of negative electrode active material). Furthermore, the use of the sintered plate can appropriately decrease the pores in the negative electrode plate (i.e., the pores lead to a reduction in capacity), and increase the energy density of the battery depending on the rate of decrease in pores.
  • the negative electrode plate 16 has a thickness of 25 ⁇ m or more, preferably 30 ⁇ m or more, more preferably 40 ⁇ m or more, particularly preferably 50 ⁇ m or more, mostly preferably 55 ⁇ m or more from the viewpoint of an increase in the active material capacity per unit area and an increase in energy density of the secondary lithium battery 10 .
  • the thickness of the negative electrode plate 16 may have any upper limit.
  • the negative electrode plate 16 has a thickness of preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less from the viewpoint of the avoidance in the deterioration of the battery properties accompanied by repeated charge/discharge cycles (particularly, due to an increase in electric resistance).
  • the negative electrode plate 16 has dimensions of preferably 5 mm by 5 mm or more, more preferably 10 mm by 10 mm or more. In another expression, the negative electrode plate 16 has an area of preferably at least 25 mm 2 , more preferably at least 100 mm 2 .
  • the ratio C/A i.e., the ratio of the capacity C of the positive electrode plate 12 to the capacity A of the negative electrode plate 16 , preferably satisfies 1.0 ⁇ C/A ⁇ 1.6, more preferably 1.005 ⁇ C/A ⁇ 1.500. Since the capacity C of the positive electrode plate 12 is larger than the capacity A of the negative electrode plate 16 as shown in the above formula, the secondary battery 10 is operated based on the capacity of the negative electrode plate 16 , resulting in a reduction in the rate of carrier metal (e.g., lithium metal) used in the positive electrode plate 12 and a decrease in the level of expansion and contraction of the positive electrode plate 12 accompanied by intercalation and deintercalation of carrier ions (e.g., lithium ions).
  • carrier metal e.g., lithium metal
  • the C/A ratio within the above range can be achieved by appropriately controlling several characteristics, such as thickness and porosity, in the positive electrode plate 12 , and several characteristics, such as thickness and porosity, in the negative electrode plate 16 .
  • the C/A ratio is preferably determined in accordance with the following procedures:
  • a practical electric capacity (mAh) for an area of 1 cm 2 of the positive electrode plate 12 is determined at 25° C. to be the capacity C of the positive electrode plate 12 .
  • the practical electric capacity is measured by the charge at a constant current of 0.2 C until the potential relative to lithium metal reaches 4.25 V and then at a constant voltage for 10 hours followed by the discharge at a constant current of 0.2 C until the potential relative to lithium metal reaches 3.0 V.
  • a practical electric capacity (mAh) for an area of 1 cm 2 of the negative electrode plate 16 is determined at 25° C. to be the capacity A of the negative electrode plate 16 .
  • the practical electric capacity is measured by the charge at a constant current of 0.2 C until the potential relative to lithium metal reaches 0.8 V and then at a constant voltage for 10 hours followed by the discharge at a constant current of 0.2 C until the potential relative to lithium metal reaches 2.0 V. (iii) The C/A ratio of the capacity C of the positive electrode plate 12 to the capacity A of the negative electrode plate 16 is calculated.
  • the positive electrode plate 12 is preferably a LiCoO 2 (LCO) sintered plate
  • the negative electrode plate 16 is preferably a Li 4 Ti 5 O 12 (LTO) sintered plate.
  • an averaged value of the orientation angles i.e., a mean orientation angle of more than 0° to 30° in the LCO positive electrode plate causes no expansion and contraction to occur in the main face direction during charge/discharge cycles, and the LTO negative electrode plate and the solid electrolyte also do not expand and contract during the charge/discharge cycles, resulting in no stress generation (in particular, the stress at the interface between the positive electrode plate 12 or negative electrode plate 16 and the inorganic solid electrolyte layer 14 ), and stable and rapid charge/discharge in high capacity.
  • Nb 2 TiO 7 sintered plate as the negative electrode plate 16
  • primary grains constituting the Nb 2 TiO 7 sintered plate are preferably oriented to reduce the expansion and contraction.
  • the inorganic solid electrolyte layer 14 may be any layer that contains the inorganic solid electrolyte and appropriately selected depending on the type of secondary battery 10 .
  • the inorganic solid electrolyte is desirably a lithium-ion-conductive material in a secondary lithium battery.
  • Preferred examples of the lithium-ion-conductive materials that can constitute the inorganic solid electrolyte layer 14 include garnet ceramic materials, nitride ceramic materials, perovskite ceramic materials, phosphate ceramic materials, sulfide ceramic materials, borosilicate ceramic materials, lithium halide materials, and polymer materials.
  • More preferred examples include at least one selected from the group consisting of garnet ceramic materials, nitride ceramic materials, perovskite ceramic materials, and phosphate ceramic materials.
  • the garnet ceramic materials include Li—La—Zr—O materials (specifically, such as Li 7 La 3 Zr 2 O 12 ) and Li—La—Ta—O materials (specifically, such as Li 7 La 3 Ta 2 O 12 ).
  • nitride ceramic materials include Li 3 N.
  • the perovskite ceramic materials include Li—La—Zr—O materials (specifically, such as LiLa 1 ⁇ x Ti x O 3 (0.04 ⁇ x ⁇ 0.14)).
  • Examples of the phosphate ceramic materials include lithium phosphate, nitrogen-substituted lithium phosphate (LiPON), Li—Al—Ti—P—O, Li—Al—Ge—P—O, and Li—Al—Ti—Si—P—O (specifically, such as Li 1+x+y Al x Ti 2 ⁇ x Si y P 3 ⁇ y O 12 (0 ⁇ x ⁇ 0.4, 0 ⁇ y ⁇ 0.6)).
  • Examples of the sulfide ceramic materials include LiOH—Li 2 SO 4 and Li 3 BO 3 —Li 2 SO 4 —Li 2 CO 3 .
  • Examples of the borosilicate ceramic materials include Li 2 O—B 2 O 3 —SiO 2 .
  • lithium halide materials examples include Li 3 OX (where X is Cl and/or Br), Li 2 (OH) 1 ⁇ a F a Cl (where 0 ⁇ a ⁇ 0.3), and Li 2 OHX (where X is Cl and/or Br), and particularly preferred is Li 3 OCl.
  • the inorganic solid electrolyte preferably has a melting point lower than the melting point or pyrolytic temperature of the positive electrode plate 12 or the negative electrode plate 16 .
  • This melting point in the electrolyte is advantageous in filling the pores in the positive electrode plate 12 and/or the negative electrode plate 16 with the inorganic solid electrolyte, as described above.
  • the inorganic solid electrolyte has a melting point that is, typically higher than the battery operational temperature, more typically above the battery operational temperature to 600° C. Based on this low melting point, the inorganic solid electrolyte can melt at a temperature of 100 to 600° C. and permeate into the pores of the positive electrode plate 12 and/or the pores of the negative electrode plate 16 as described later, resulting in strong interfacial contact.
  • the solid electrolyte preferably contains a lithium halide material.
  • the lithium halide materials include, preferably at least one selected from the group consisting of Li 3 OCl, Li (3 ⁇ x) M x/2 OA (where 0 ⁇ x ⁇ 0.8, M is at least one selected from the group consisting of Mg, Ca, Ba and Sr, and A is at least one selected from the group consisting of F, Cl, Br and I), Li 2 (OH) 1 ⁇ a F a Cl (where 0 ⁇ a ⁇ 0.3), and Li 2 OHX (where X is Cl and/or Br), and more preferably Li 3 OCl or Li 2 (OH) 0.9 F 0.1 Cl.
  • Each material as described above is advantageous in high ion conductivity.
  • LiPON lithium phosphate oxynitride ceramic materials
  • the LiPON is a group of compounds represented by, for example, a formula Li a PO b N c (where a is 2 to 4, b is 3 to 5, and c is 0.1 to 0.9), particularly a formula Li 2.9 PO 3.3 NO 0.46 .
  • the inorganic solid electrolyte layer 14 can be produced by any process. Suitable examples of such processes include vapor phase deposition, such as sputtering and CVD; liquid phase deposition, such as screen printing and spin coating; compression of powder; heating of a raw material to a temperature above the melting point and then solidification of the melt; and heating of compressed raw powder to a temperature above the melting point and then solidification of the melt.
  • vapor phase deposition such as sputtering and CVD
  • liquid phase deposition such as screen printing and spin coating
  • compression of powder heating of a raw material to a temperature above the melting point and then solidification of the melt
  • heating of compressed raw powder to a temperature above the melting point and then solidification of the melt.
  • the solid electrolyte 14 may have any dimension.
  • the solid electrolyte has a thickness of preferably 0.0005 mm to 1.0 mm, more preferably 0.001 mm to 0.1 mm, further more preferably 0.002 to 0.05 mm from the viewpoint of high-rate performance during charge/discharge cycles and mechanical strength.
  • the thickness of the solid electrolyte layer may be controlled by a layering process, or with spacers in the case of heating of compressed raw powder to a temperature above the melting point and then solidification of the melt.
  • the all-solid lithium battery preferably includes spacers for defining the thickness of the solid electrolyte layer 14 between the oriented positive electrode plate 12 and the negative electrode plate 16 .
  • the spacers have an electrical resistivity of preferably 1 ⁇ 10 5 ⁇ cm or more, and more preferably 1 ⁇ 10 7 ⁇ cm or more.
  • the spacers are composed of any material, preferably composed of ceramic, such as Al 2 O 3 , MgO, and ZrO 2 .
  • the thickness Te of the inorganic solid electrolyte layer, the thickness Tc of the positive electrode plate, and the thickness Ta of the negative electrode plate satisfy preferably Te/(Tc+Ta) ⁇ 0.25, more preferably 0.002 ⁇ Te/(Tc+Ta) ⁇ 0.25, further more preferably 0.005 ⁇ Te/(Tc+Ta) ⁇ 0.2.
  • the inorganic solid electrolyte layer has a significantly small thickness Te compared to the total thickness Ta+Tc of the positive electrode plate and the negative electrode plate, resulting in a significantly high energy density of the secondary battery 10 .
  • One face, remote from the solid electrolyte 14 , of the positive electrode plate 12 is preferably provided with a positive electrode collector 13 .
  • the other face, remote from the solid electrolyte 14 , of the negative electrode plate 16 is preferably provided with a negative electrode collector 17 .
  • the materials constituting the positive electrode collector 13 and the negative electrode collector 17 include platinum (Pt), platinum (Pt)/palladium (Pd), gold (Au), silver (Ag), aluminum (Al), copper (Cu), ITO (indium-tin oxide film), and nickel (Ni).
  • the positive electrode plate 12 , the inorganic solid electrolyte 14 , and the negative electrode plate 16 are accommodated in a container 26 .
  • the container 26 may be of any type that can accommodate a unit cell or a laminated battery including a stack of multiple unit cells electrically connected in series or in parallel.
  • the container 26 since a secondary battery 10 has no risk of electrolyte leakage, the container 26 may be of a relatively simple type, and the cell or battery may be packaged with a cover material.
  • the cell or battery can be manufactured in a chip form for mounting on an electronic circuit or in a laminate cell form (e.g., a multilayer product of aluminum (Al)/polypropylene (PP)) for low-profile and broad space applications.
  • the positive electrode collector 13 and/or the negative electrode collector 17 may have a structure that can serve as a part of the container 26 .
  • a heat-resistant resin such as polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), polyimide, and polyamide, may be used in place of polypropylene, and a metal, such as aluminum or stainless steel, may also be used after ensuring insulation between the cover material and the collector.
  • the inventive secondary battery 10 is preferably produced as follows: Inorganic solid electrolyte powder having a melting point lower than the melting point or pyrolytic temperature of the positive electrode plate 12 (or the negative electrode plate 16 ) is placed on the positive electrode plate 12 (or the negative electrode plate 16 ). The negative electrode plate 16 (or the positive electrode plate 12 ) is placed on the inorganic solid electrolyte powder. The negative electrode plate 16 is pressed toward the positive electrode plate 12 (or the positive electrode plate is pressed toward the negative electrode plate) at 100 to 600° C., preferably 200 to 500° C., more preferably 250 to 450° C. to melt the solid electrolyte powder and permeate the melt into the pores in the positive electrode plate.
  • This press treatment is performed by any process that can generate a load, for example, a mechanical load or weight. Subsequently, the positive electrode plate 12 , the molten electrolyte, and the negative electrode plate 16 are spontaneously or controllably cooled to solidify the molten electrolyte into the solid electrolyte 14 .
  • Preferred examples of the inorganic solid electrolyte powder having a melting point lower than the melting point or pyrolytic temperature of the positive electrode plate 12 (or the negative electrode plate 16 ) include powder containing at least one selected from the group consisting of xLiOH.yLi 2 SO 4 , Li 3 OCl, Li (3 ⁇ x) M x/2 OA, Li 2 (OH) 1 ⁇ a F a Cl, Li 2 OHX, and Li a (OH) b F c Br.
  • the all-solid lithium battery 10 may include spacers that define the thickness of the solid electrolyte layer 14 between the positive electrode plate 12 and the negative electrode plate 16 . This configuration is preferably achieved by disposing spacers along with the solid electrolyte powder between the oriented positive electrode plate 12 and the negative electrode plate 16 .
  • LiCoO 2 is abbreviated as “LCO” and Li 4 Ti 5 O 12 is abbreviated as “LTO”.
  • Co 3 O 4 powder available from Seido Chemical Co., Ltd., a mean particle size of 0.9 ⁇ m
  • Li 2 CO 3 powder available from The Honjo Chemical Corporation
  • the resultant powder was pulverized in a pot mill into a volume-based D50 of 0.4 ⁇ m to give LCO powder composed of platy particles.
  • BM-2 available from Sekisui Chemical Co., Ltd.
  • a plasticizer di-2-ethylhexyl phthalate (DOP), available from Kurogane Kasei Co., Ltd.
  • a dispersant product name: RHEODOL SP-O30, available from Kao Corporation (2 parts by weight) (2 parts by weight) were mixed.
  • the mixture was defoamed by stirring under reduced pressure to prepare an LCO slurry with a viscosity of 4000 cP.
  • the viscosity was measured with an LVT viscometer available from Brookfield.
  • the slurry was molded into an LCO green sheet onto a PET film by a doctor blade process. The thickness of the LCO green sheet was adjusted such that the fired thickness was 25 ⁇ m (Example A1) or 200 ⁇ m (Examples A2 to A5 and A7).
  • Li 2 CO 3 raw material powder (volume-based particle diameter D50: 2.5 ⁇ m, available from The Honjo Chemical Corporation) (100 parts by weight), a binder (poly(vinyl butyral): Product No. BM-2, available from Sekisui Chemical Co., Ltd.) (5 parts by weight), a plasticizer (di-2-ethylhexyl phthalate (DOP), available from Kurogane Kasei Co., Ltd.) (2 parts by weight), and a dispersant (RHEODOL SP-O30, available from Kao Corporation) (2 parts by weight) were mixed. The mixture was defoamed by stirring under reduced pressure to prepare a Li 2 CO 3 slurry with a viscosity of 4000 cP.
  • a binder poly(vinyl butyral): Product No. BM-2, available from Sekisui Chemical Co., Ltd.
  • DOP di-2-ethylhexyl phthalate
  • RHEODOL SP-O30 available
  • the viscosity was measured with an LVT viscometer available from Brookfield.
  • the Li 2 CO 3 slurry was molded into a Li 2 CO 3 green sheet on a PET film by a doctor blade process.
  • the dried thickness of the Li 2 CO 3 green sheet was adjusted such that the Li/Co molar ratio of the Li content in the Li 2 CO 3 green sheet to the Co content in the LCO green sheet is a predetermined value.
  • the LCO green sheet was separated from the PET film, and was cut into a 50 mm square. The cut piece was placed on the center of a bottom magnesia setter (dimensions: 90 mm square, height: 1 mm). The LCO green sheet was heated to 600° C. at a heating rate of 200° C./h, and was degreased for three hours. The LCO green sheet was then kept at 900° C. for three hours to calcine the LCO green sheet. The dried Li 2 CO 3 green sheet was cut into a size such that the Li/Co molar ratio of the Li content in the Li 2 CO 3 green sheet to the Co content in the calcined LCO plate was 0.5.
  • the laminate was heated to 600° C. at a heating rate of 200° C./h, and was degreased for three hours. The laminate was then heated to 800° C. at 200° C./h, and was kept for five hours.
  • the laminate was then heated to 900° C. at 200° C./h, and was kept for 24 hours to be fired. After the firing, the fired laminate was cooled to room temperature, and was removed from the alumina sheath. Thus, the sintered LCO plate was yielded as a positive electrode plate.
  • An Au film (a thickness of 100 nm) was deposited by sputtering on a face, in contact with the bottom setter, of the sintered LCO plate, and the LCO positive electrode plate was then cut into a 10 mm by 10 mm by a laser process.
  • a dispersant product name: Rheodor SP-O30, available from Kao Corporation
  • the resultant mixture of raw materials for the negative electrode was stirred and defoamed under reduced pressure, and then the viscosity was adjusted to 4000 cP to prepare an LTO slurry.
  • the viscosity was measured with an LVT viscometer available from Brookfield.
  • the resulting slurry was applied onto a PET film by a doctor blade process into an LTO green sheet.
  • the dried thickness of LTO green sheet was adjusted such that the fired thickness was 28 ⁇ m (Example A1), 224 ⁇ m (Examples A2 and A3), 257 ⁇ m (Example A4) or 161 ⁇ m (Example A5).
  • the resultant green sheet was cut into a 25 mm square with a box cutter and placed onto an embossed zirconia setter.
  • the green sheet on the setter was placed into an alumina sheath and held at 500° C. for five hours, then heated at a rate of 200° C./h and fired at 800° C. for five hours.
  • An Au film (a thickness of 100 nm) as a current collecting layer was deposited on a face, in contact with the setter, of the resultant LTO sintered plate by sputtering, and the LTO sintered plate was then cut into a 10 mm by 10 mm by a laser process.
  • An aqueous raw material solution was prepared by dissolving of LiOH (4.790 g) and LiCl (4.239 g) into a small amount of deionized water. Each amount of these precursors was determined such that the stoichiometric ratio corresponded to the reactant formula: Li 3 OCl+H 2 O. Most of the water was removed with a rotary evaporator and a bath at about 90° C. The resulting solid was placed in an alumina boat. The boat was disposed in an electric furnace and heated in vacuum at about 280° C. for about 48 hours to give Li 3 OCl powder, which is a reaction product, as an inorganic solid electrolyte.
  • the Li 3 OCl powder was placed on the positive electrode plate; the positive electrode plate and the Li 3 OCl powder were heated at 400° C. on a hot plate; and the negative electrode plate was placed while being pressed from the top. At this time, the Li 3 OCl powder was melted followed by solidification, and a solid electrolyte layer having a thickness of 20 ⁇ m was thereby formed.
  • the unit cell composed of the positive electrode plate, the solid electrolyte layer and the negative electrode plate was used to prepare a laminated battery.
  • the sintered LCO plate was polished with a cross section polisher (CP) (IB-15000CP, available from JEOL Ltd.), and the resultant cross-section of the positive electrode plate (cross-section perpendicular to a main face of the positive electrode plate) was subjected to the EBSD measurement at a 1000-fold field of view (125 ⁇ m by 125 ⁇ m) to give an EBSD image.
  • CP cross section polisher
  • This EBSD measurement was performed using a Schottky field emission scanning electron microscope (model JSM-7800F, available JEOL Ltd.).
  • the angle defined by the (003) plane of the primary grain and the main face of the positive electrode plate i.e., the tilt of the crystal orientation from the (003) plane
  • the mean value of the angles was determined as a mean orientation angle (i.e., a mean tilt angle) of the primary grains.
  • the LCO positive electrode plate and the LTO negative electrode plate were each polished with a cross section polisher (CP) (IB-15000CP, available from JEOL Ltd.), and the resultant cross-section of each electrode plate was observed with an SEM (JSM6390LA, available from JEOL Ltd.) to determine the thickness of each electrode plate.
  • CP cross section polisher
  • Each of the LCO positive electrode plate and the LTO negative electrode plate was polished with a cross section polisher (CP) (IB-15000CP, available from JEOL Ltd.), and the resultant cross-section of each electrode plates was observed with a SEM (JSM6390LA, available from JEOL Ltd.) at a 1000-fold field of view (125 ⁇ m by 125 ⁇ m). The image analysis was then performed, and the porosity (%) of each electrode plate was determined through dividing the area of all the pores by the total area of each plate and multiplying the resulting value by 100.
  • CP cross section polisher
  • the LCO positive electrode plate is polished with a cross section polisher (CP) (IB-15000CP, available from JEOL Ltd.), and the cross-section of the positive electrode plate was observed with an SEM (JSM6390LA, available from JEOL Ltd.) at a 1000-fold field of view (125 ⁇ m by 125 ⁇ m).
  • CP cross section polisher
  • SEM JSM6390LA, available from JEOL Ltd.
  • the resultant SEM image was binarized using image analysis software, ImageJ, and pores were identified in the binary image.
  • the aspect ratio was calculated through dividing the length in the longitudinal direction by the length in the lateral direction. The aspect ratios were calculated for all the pores in the binary image and averaged into a mean aspect ratio.
  • a practical electric capacity (mAh) for an area of 1 cm 2 of the positive electrode plate was determined at 25° C. to be the capacity C of the positive electrode plate.
  • the practical electric capacity was measured through the charge at a constant current of 0.2 C until the potential relative to lithium metal reached 4.25 V and then at a constant voltage for 10 hours followed by the discharge at a constant current of 0.2 C until the potential relative to lithium metal reached 3.0 V.
  • a practical electric capacity (mAh) for an area of 1 cm 2 of the negative electrode plate was determined at 25° C. to be the capacity A of the negative electrode plate.
  • the practical electric capacity is measured by the charge at a constant current of 0.2 C until the potential relative to lithium metal reached 0.8 V and then at a constant voltage for 10 hours followed by the discharge at a constant current of 0.2 C until the potential relative to lithium metal reached 2.0 V.
  • a C/A ratio of the capacity C of the positive electrode plate to the capacity A of the negative electrode plate is calculated.
  • the cycle capacity retention of the battery was measured in a potential range of 2.7 V to 1.5 V at a battery operational temperature of 100° C. or 300° C. in accordance with the following procedures.
  • a battery was prepared and evaluated as in Example A2 except that the negative electrode plate was produced as follows. The results are shown in Table 1.
  • BM-2 available from Sekisui Chemical Co., Ltd. (20 parts by weight), a plasticizer (di-2-ethylhexyl phthalate (DOP), available from Kurogane Kasei Co., Ltd.) (4 parts by weight), and a dispersant (product name: RHEODOL SP-O30, available from Kao Corporation) (2 parts by weight) were mixed.
  • DOP di-2-ethylhexyl phthalate
  • RHEODOL SP-O30 available from Kao Corporation
  • the Nb 2 TiO 7 slurry was molded into a sheet on a PET film by a doctor blade process to give a Nb 2 TiO 7 green sheet.
  • the dried thickness of the Nb 2 TiO 7 green sheet was adjusted such that the fired thickness was 100 ⁇ m.
  • the resultant green sheet was cut into a 25 mm square with a box cutter, and the cut sheet was placed on an embossed zirconia setter.
  • the green sheet on the setter was placed into an alumina sheath, kept at 500° C. for five hours, and then heated at a rate of 200° C./h and fired at 1100° C. for five hours.
  • An Au film (a thickness of 100 nm) was deposited on a face, in contact with the setter, of the sintered Nb 2 TiO 7 sintered plate by sputtering, and the sintered plate was then cut into a 10 mm by 10 mm by a laser process.
  • a battery was prepared and evaluated as in Example A2 except that the battery operational temperature was 25° C. The results are shown in Table 1.
  • LTO indicates Li 4 Ti 5 O 12 .
  • Co 3 O 4 powder (a mean particle size of 0.3 ⁇ m) and commercially available Li 2 CO 3 powder (a D50 particle size of 2.5 ⁇ m) weighed into a Li/Co molar ratio of 1.02 were mixed, and the mixture was kept at 750° C. for five hours.
  • the resultant powder was pulverized in a pot mill into a volume-based D50 of 1 ⁇ m or less to give LCO powder composed of platy particles.
  • the mixture was defoamed by stirring under reduced pressure to prepare an LCO slurry with the adjusted viscosity.
  • the resultant slurry was molded into an LCO green sheet onto a PET film by a doctor blade process.
  • the thickness of the LCO green sheet was adjusted such that the fired thickness was 200 ⁇ m.
  • the mixture was defoamed by stirring under reduced pressure to prepare a Li 2 CO 3 slurry with an adjusted viscosity.
  • the resultant Li 2 CO 3 slurry was molded into a Li 2 CO 3 green sheet on a PET film by a doctor blade process.
  • the dried thickness of the Li 2 CO 3 green sheet was adjusted such that the Li/Co molar ratio of the Li content in the Li 2 CO 3 green sheet to the Co content in the LCO green sheet was a predetermined value.
  • the LCO green sheet was separated from the PET film, and was cut into a 50 mm square. The cut piece was placed on the center of a bottom magnesia setter. The LCO green sheet was heated to 600° C. at a heating rate of 200° C./h, and was degreased for three hours. The LCO green sheet was then kept at 900° C. for three hours to be calcined. The dried Li 2 CO 3 green sheet was cut into a size such that the Li/Co molar ratio, which was the Li content in the Li 2 CO 3 green sheet to the Co content in the calcined LCO plate, was 0.5.
  • the cut piece of the Li 2 CO 3 green sheet which is an excess-lithium source, was placed on the calcined LCO plate, and a porous top magnesia setter was placed thereon.
  • the calcined LCO plate and the green sheet piece disposed between the top and bottom setters were placed into an alumina sheath having 120 mm square. At this time, the alumina sheath was loosely capped with a small gap.
  • the resultant laminate was heated to 600° C. at a heating rate of 200° C./h, and was degreased for three hours.
  • the laminate was then heated to 800° C. at 200° C./h, and was kept for five hours.
  • the laminate was then heated to 900° C.
  • the sintered LCO plate was yielded as a positive electrode plate.
  • An Au film (a thickness of 100 nm) was deposited on a face, in contact with the bottom setter, of the sintered LCO plate by sputtering, and the LCO positive electrode plate was then cut into a 10 mm by 10 mm by a laser process.
  • the resultant mixture of raw materials for the negative electrode was defoamed by stirring under reduced pressure to prepare an LTO slurry with the adjusted viscosity.
  • the resulting slurry was molded into an LTO green sheet onto a PET film by a doctor blade process. The dried thickness of the LTO green sheet was adjusted such that the fired thickness was 200 ⁇ m.
  • the resultant green sheet was cut into a 25 mm square with a box cutter and placed onto an embossed zirconia setter.
  • the green sheet on the setter was placed into an alumina sheath and held at 500° C. for five hours, then heated at a rate of 200° C./h and fired at 800° C. for five hours.
  • An Au film (a thickness of 100 nm) as a current collecting layer was deposited on a face, in contact with the setter, of the resultant LTO sintered plate by sputtering, and the LTO sintered plate was then cut into a 10 mm by 10 mm by a laser process.
  • LiOH purity ⁇ 98.0%
  • Li 2 SO 4 purity ⁇ 98.0%
  • These raw materials are weighed into a LiOH:Li 2 SO 4 molar ratio of 3.0:1.0 and mixed in an Ar atmospheric glove box having a dew point of ⁇ 50° C. or lower.
  • the mixture was placed in a glass tube in an Ar atmosphere and melted by heating at 430° C. for two hours.
  • the glass tube was then placed into water and kept for ten minutes, and the melt was quenched to form a solidified material.
  • the solidified material was then pulverized in a mortar in an Ar atmosphere to give 3LiOH.Li 2 SO 4 powder, which is a solid electrolyte.
  • a LiOH—Li 2 SO 4 powder containing ZrO 2 beads (5 wt %) having a diameter of 30 ⁇ m was placed on the positive electrode plate, and the negative electrode plate was then placed on the powder.
  • the resulting unit cells composed of the positive electrode plate, the solid electrolyte, and the negative electrode plate were used to produce a laminated battery.
  • the mean orientation angle of the primary grains in the positive electrode plate was measured as in Example A1.
  • the thickness of the positive electrode plate and the negative electrode plate was each measured as in Example A1.
  • the porosity of the positive electrode plate and the negative electrode plate was each measured as in Example A1. Although the pores may be partially filled with the inorganic solid electrolyte in Example B1, the term “porosity” in this specification indicates the substantial porosity that also includes portions filled with the inorganic solid electrolyte in the pores throughout the positive electrode plate, unless otherwise specified.
  • the cross-sectional SEM image used in the measurement of porosity was analyzed, and the filling rate of electrolyte (%) was calculated through dividing the area of the inorganic solid electrolyte filled in all the pores by the total area of the pores and multiplying the resulting value by 100.
  • a practical electric capacity (mAh) for an area of 1 cm 2 of the positive electrode plate was determined at 25° C. to be the capacity C of the positive electrode plate as in Example A1.
  • the discharge capacity of the battery was measured at an operational temperature of 100° C. in the voltage range of 2.7 V to 1.5 V in accordance with the following procedures.
  • the charge/discharge cycles included the charge under constant current at a rate of 1 C until the voltage reached the upper limit and then under constant voltage until the current reached a rate of 0.2 C, followed by the discharge at a rate of 0.2 C until the voltage reached the lower limit.
  • the cycles were repeated three times, and the discharge capacities were measured at each time and averaged to be a mean discharge capacity.
  • the rate of the mean discharge capacity to the practical electric capacity (mAh) of the positive electrode plate was calculated to be a discharge capacity rate (%).
  • a battery was prepared and evaluated as in Example B1 except that a positive electrode plate and a negative electrode plate were produced as follows:
  • LiCoO 2 powder (a D50 particle size of 7 ⁇ m) was uniaxially compressed at 100 MPa in a mold to prepare a LiCoO 2 shaped material. The thickness of the shaped material was determined such that the fired thickness was 200 ⁇ m.
  • the LiCoO 2 shaped material was disposed on an alumina setter, and placed into an alumina sheath. At this time, the alumina sheath was loosely capped with a small gap.
  • the resultant laminate was heated to 925° C. at a heating rate of 200° C./h and kept for 20 hours to be fired. After the firing, the laminate was cooled to room temperature, and the fired laminate was removed from the alumina sheath to give a LiCoO 2 sintered plate, which was a positive electrode plate.
  • An Au film (a thickness of 100 nm) was deposited as a current collecting layer on one face of the LiCoO 2 sintered plate by sputtering.
  • a sintered LTO plate was produced as in Example B1 except that another LTO powder (a D50 particle size of 0.7 ⁇ m) was used in Procedure (2a).
  • a battery was prepared and evaluated as in Example B1 except that a positive electrode plate and a negative electrode plate were produced as follows:
  • An LCO sintered plate was produced as in Example B2 except that the firing temperature was 775° C.
  • An LTO sintered plate was produced as in Example B2 except that the firing temperature was 750° C.
  • a battery was prepared and evaluated as in Example B1 except that a positive electrode plate and a negative electrode plate were produced as in Example B2 and the heating in the electric furnace was performed at 380° C. for 45 minutes in Procedure (4).
  • a battery was prepared and evaluated as in Example B1 except that a positive electrode plate was produced as follows and a negative electrode plate was produced as in Example B2:
  • An LCO sintered plate was produced as in Example B1 except that another Co 3 O 4 powder (a mean particle size of 0.9 ⁇ m) was used in Procedure (1a), and the Li/Co molar ratio, indicating the Li content in the Li 2 CO 3 green sheet placed on the calcined LCO plate, was 0.1 and the maximum temperature was 850° C. in Procedure (1c).
  • a battery was prepared and evaluated as in Example B1 except that a positive electrode plate and a negative electrode plate were produced as follows:
  • An LCO sintered plate was produced as in Example B1 except that the Li/Co ratio was 0.6 and the firing was performed at a maximum temperature of 900° C. for 24 hours in Procedure (1c).
  • An LTO sintered plate was produced as in Example B1 except that the firing was performed at a maximum temperature of 800° C. for 10 hours in Procedure (2b).
  • a battery was prepared and evaluated as in Example B1 except that a positive electrode plate and a negative electrode plate were produced as in Example B2, Li(OH) 0.9 F 0.1 Cl powder produced as follows was used in the solid electrolyte and the solid electrolyte powder was heated at 350° C. for 45 minutes in Procedure (4).
  • LiOH purity ⁇ 98.0%
  • LiCl purity ⁇ 99.9%
  • each raw material was weighed into a LiOH:LiCl:LiF molar ratio of 0.9:1.0:0.1 and mixed.
  • the resultant mixed powder was transferred into a crucible made of alumina, and the crucible was placed in a quartz tube and sealed with a flange. This quartz tube was fixed in a tubular furnace and heated at 350° C. for 30 minutes. During this heating, an Ar gas having a dew point of ⁇ 50° C.
  • the heating temperature and time in an Ar gas atmosphere can be modified as appropriate. In general, the heating temperature should be 250° C. to 600° C., and the heating time should be 0.1 hours or longer.
  • a battery was prepared and evaluated as in Example B1 except that a positive electrode plate and a negative electrode plate were produced as in Example B2, Li(OH) 0.9 F 0.1 Br powder produced as follows was used in the solid electrolyte, and the solid electrolyte powder was heated at 350° C. for 45 minutes in Procedure (4).
  • LiOH purity ⁇ 98.0%
  • LiBr purity ⁇ 99.9%
  • each raw material was weighed into a LiOH:LiBr:LiF molar ratio of 0.9:1.0:0.1 and mixed.
  • the resultant mixed powder was transferred into a crucible made of alumina, and the crucible was placed in a quartz tube, and sealed with a flange. This quartz tube was fixed in a tubular furnace and heated at 350° C. for 30 minutes. During this heating, an Ar gas having a dew point of ⁇ 50° C.
  • the heating temperature and time in an Ar gas atmosphere can be changed as appropriate. In general, the heating temperature should be 250° C. to 600° C., and the heating time should be 0.1 hours or longer.
  • a battery was prepared and evaluated as in Example B1 except that an LNMO sintered plate produced as follows was used in the positive electrode plate, a negative electrode plate was produced as follows, and the C/A ratio and the discharge capacity rate were measured as follows:
  • Li 2 CO 3 powder, NiO powder, and MnO 2 powder were weighed and mixed such that LiNi 0.5 Mn 1.5 O 4 was synthesized after firing.
  • the mixture was placed into an alumina sheath, heated at 200° C./h and kept at a maximum temperature of 900° C. for four hours, and then kept at 650° C. for four hours followed by cooling at 200° C./h.
  • the resultant powder was pulverized in a mortar and a pot mill such that D50 reached 5 ⁇ m or less, and then heated again in the same manner as above.
  • the resultant composite material was pulverized into a volume-based D50 of 1 ⁇ m or less to give an LNMO powder.
  • the mixture was stirred by defoaming under reduced pressure to prepare an LNMO slurry with the adjusted viscosity.
  • the resultant slurry was molded into an LNMO green sheet onto a PET film by a doctor blade process. The thickness of the LNMO green sheet was adjusted such that the fired thickness was 200 ⁇ m.
  • the LNMO green sheet peeled from the PET film was cut into a 50 mm square with a cutter, placed on the center of a bottom magnesia setter, and a porous top magnesia setter was placed on the LNMO green sheet.
  • the cut piece of green sheet disposed between two setters was placed in an alumina sheath. At this time, the alumina sheath was loosely capped with a small gap.
  • the resultant laminate is heated to 600° C. at a rate of 200° C./h, and degreased for three hours.
  • the laminate was then heated to 900° C. at 200° C./h and kept for five hours, and kept at 650° C.
  • an LNMO sintered plate which was a positive electrode plate.
  • An Au film (a thickness of 100 nm) as a current collecting layer was deposited on a face, in contact with the bottom setter, of the resultant LNMO sintered plate by sputtering, and the LNMO sintered plate was then cut into a 10 mm by 10 mm by a laser process.
  • An LTO sintered plate was produced as in Example B2 except that the fired thickness was 150 ⁇ m.
  • a practical electric capacity (mAh) for an area of 1 cm 2 of the positive electrode plate was determined at 25° C. to be the capacity C of the positive electrode plate.
  • the practical electric capacity is measured by the charge at a constant current of 0.2 C until the potential relative to lithium metal reached 4.9 V and then at a constant voltage for 10 hours followed by the discharge at a constant current of 0.2 C until the potential relative to lithium metal reached 3.0 V.
  • the discharge capacity rate (%) was determined as in Example B1 except that the voltage range of the charge/discharge cycle was 3.4 V to 1.5 V.
  • a battery was prepared and evaluated as in Example B1 except that an NCM sintered plate produced as follows was used in a positive electrode plate, a negative electrode plate was produced as in Example B2, and the C/A ratio and the discharge capacity rate were measured as follows:
  • NCM (523) shaped material was determined such that the fired thickness was 200 ⁇ m.
  • the NCM (523) shaped material was disposed on an alumina setter, and placed into an alumina sheath. At this time, the alumina sheath was loosely capped with a small gap.
  • the resultant laminate was heated to 920° C. at a heating rate of 200° C./h and kept for 10 hours to be fired. After the firing, the fired material was retrieved from the alumina sheath after cooling to room temperature to give an NCM (523) sintered plate, which was a positive electrode plate.
  • An Au film (a thickness of 100 nm) as a current collecting layer was deposited on a face of the resultant NCM (523) sintered plate by sputtering.
  • a practical electric capacity (mAh) for an area of 1 cm 2 of the positive electrode plate was determined at 25° C. to be the capacity C of the positive electrode plate.
  • the practical electric capacity is measured by the charge at a constant current of 0.2 C until the potential relative to lithium metal reached 4.25 V and then at a constant voltage for 10 hours followed by the discharge at a constant current of 0.2 C until the potential relative to lithium metal reached 3.0 V.
  • the discharge capacity rate (%) was determined as in Example B1 including the voltage range of charge/discharge cycles.
  • LCO indicates LiCoO 2
  • LNMO indicates LiNi 0.5 Mn 1.5 O 4
  • NCM indicates LiNi 0.5 Co 0.2 Mn 0.3 O 2
  • LTO indicates Li 4 Ti 5 O 12 .
  • the battery operational temperature is 100° C. in all Examples.

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